Production of carbon chloride compounds of the formula c4cl6



Patented Jan. 13, 1942 PRODUCTION OF CARBON CHLORIDE COM- POUNDS OF THE FORMULA C4018 Martin Mugdan, Munich, Bavaria, and Josef Wlmmer, Burghausen, upper Bavaria. Germany, assignors to Consortium fur Elektrochemische Industrie, G. m..b. 11., Munich, Bavaria, Germany, a corporation of Germany No Drawing. Application March 31, 1938, Serial In Germany April 1'1, 1937 13 Claims. (01.260-6551 This invention relates to a novel carbon-chloride compound of the formula C4C1c and to a process for producing same.

We have found 4 that hexachlorbutene (C4H2Cls), which 'is generated by heating trichlorethylene under pressure as disclosed in our application Serial No. 117,903, filed December 28, 1936, quickly splits oil a mol of HCl under treatment with certain metal chlorides at an elevated temperature and goes over into the compound C4HC15, which is largely pentachlorbutadien.

This last mentioned compound can be transformed into heptachlorbutene (CAHCI'I) by treatment with chlorine in the presence of chlorine carriers, preferably chloride of antimony. The heptachlorbutene has the property of splitting off another mol of HCl by further treatment with metal chlorides. Our new carbon-chloride compound of the formula C4Clc is generated during the process. These reactions involving the alternate splitting off of HCl and the addition of chlorine occur with almost quantitative yield.

- We have found that it is not necessary. to produce a pure intermediate body, since the chloride catalysts do not adversely afiect one another. Chlorination may be effected quite readily after the HCl dissociation from hexachlorbutene in the presence of a chlorinating agent such as a small quantity of chloride of antimony, and thereafter HCl may be split ofi' again at a somewhat higher temperature. Accordingly it is quite possible to perform the operation of the HCl dissociatlons and the chlorine addition simultaneously by treating hexachlorbutene at an elevated temperature and with simultaneous use of both catalysts with chlorine, whereby the carbonchloride end product is generated without an in-- termediate operation with HCl dissociation. It is, however, preferable to allow the process to take place in successive steps so as to obtain the hydrochloric acid entirely free from chlorine and so as not to impair the chlorine addition through the HCl dissociation. Moreover, it is also possible to chlorinate the hexachlorbutene in the first place, whereby octachlorbutane (CiHZClS) is produced, and to transform this by treatment with the HCl-dissociation catalyst into the C4016, whereby twomolecules of 1101 are, split off.

For the HCl dissociation, chloride compounds of iron, cobalt and manganese are particularly suitable.

Ill

Example 1 1 mol (262 g.) hexachlorbutene was heated .with 0.5 g. ferric chloride to a temperature'of- 70-140 0. After about two hours 1 mol HCl was split off. Thereupon 0.3 g. of antimony-chloride was added, and, while stirring, chlorine was added at about 70 0. During the heat development chlorine in the amount of 71 g. was quickly taken up.' After the termination of the chlorine takeup, the temperature was raised to 140 to 200 C. A further mol of HCl was split 011 during this step of the process. Finally the product, C4016, was freed from the catalysts with diluted hydrochloric acid and water, and distilled. It distilled over under 712 mm'. at 211+212 C.

Example 2 1 mol hexachlorbutene was mixed with-0.3 g. chloride of antimony, and treated with chlorine at 8090 C. while being stirred. '71 g. chlorine were taken up in three hours. The octachlorbutane' which was produced was then mixed with g 0.5 g. ferric chloride, and heated to 120-200 C; In about two. hours 2 mols 1101 were split off. The carbon-chloride compound thus obtained was found to be identical with that obtained according to Example 1.

Example 3 1 mol hexachlorbutene wasmixed with 0.5 g.

,CiCls' boils without disintegration at 211 C. (710 mm.), 2115 C. (760 mm); melting point .-21." C. This C4C1s is not changed by heating to temperatures far above the boiling point under pressure, and it is very resistant to metals, to concentrated min'eral acids and to aqueous alkali solutions even at elevated temperatures- C4016 may be used as 'a non-inflammable solvent, as a substitute for or addition to mineral oils in all situations in which mineral oilsare used except for combustion purposes, as heat transfer means and the like, as well as forchemical ulterior treatments.

The invention claimed is: 1

-1. The process for producing a carbon chloride of the formula 0401s from hexachlorbutene which comprises adding two atoms of chlorine by treatment with chlorine in the presence of a chlorination catalyst and removing two molecules of hydrogen chloride by treatment with a dehydrochlorination catalyst. the individual chlorination and dehydrochlorination steps being carried out in any order.

2. The process for producing a carbon chloride of the formula C4Clo from hexachlorbutene which comprises adding two atoms of chlorine by treatment with chlorine in the presence of a chlorination catalyst and removing two molecules of hydrogen chloride by treatment with a dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and manganese, the individual chlorination and dehydrochlorination steps being carried out in any order.

3. The process for producing a carbon chloride of the formula C4C1s from hexachlorbutene which comprises adding two atoms of chlorine by treatment with chlorine in the presence of antimony chloride as a chlorination catalyst and removing two molecules of hydrogen chloride by treatment with a dehydrochlorination catalyst, the individual chlorination and dehydrochlorination steps being carried out in any order.

4., The process for producing a carbon chloride of the formula C4Clo from hexachlorbutene which comprises adding two atoms of chlorine by treatment with chlorine in the presence of antimony chloride as a chlorination catalyst and removing two molecules of hydrogen chloride by treatment with a dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and mangan'ese, the individual chlorination and dehydrochlorination steps being carried out in any order.

5. The process of producing a carbon compound of the formula 0401s which comprises heating hexachlorbutene at a temperature between 70 C. and 140 C. in the presence of a dehydrochlorination catalyst until one molecule of hydrogen chloride is split off, treating the resulting pentachlorbutadiene with chlorine in the presence of a chlorination catalyst at a temperature of about 70 0., and heating the resulting heptachlorbutene to a temperature between 140 C and 200 C. in the presence of a dehydrochlorination catalyst until another molecule of hydrogen chloride is split oil.

6. The process of producing a carbon compound of the formula C4C1e which comprises heating hexachlorbutene at a temperature between 70 C. and 140 C. in the presence of a dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and manganese until one molecule of hydrogen chloride is split off, treating the resulting pentachlorbutadiene with chlorine in the presence of a chlorination catalyst at a temperature of about 70 0., and heating the resulting heptachlorbutene to a temperature between 140 C. and 200 C. in the presence of a dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and manganese until another molecule of hydrogen chloride is split off.

7. The process of producing a carbon comound of the' formula C4Clc which comprises tween 70 0. and 140 C. in the presence of a. dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and manganese until one molecule of hydrogen chloride is split oil, treating the resulting pentachlorbutadiene with chlorine in the presence of antimony chloride as a chlorination catalyst at a temperature of about 70 0., and heating the resulting heptachlorbutene to a temperature between 140 C. and 200 C. in the presence of a dehydrochlorination catalyst selected from the groupwconsisting of the chloride compounds of iron, cobalt and manganese until another molecule of hydrogen chloride is split off.

8. The process of producing a carbon compound of the formula C4Cle which comprises heating hexachlorbutene at a temperature between 70 C. and 140 0. in the presence of a dehydrochlorination catalyst until one molecule of hydrogen chloride is split off, adding to the resulting mixture of the dehydrochlorination catalyst and pentachlorbutadiene antimony chloride as a chlorination catalyst, adding chlorine to such mixture while heating the mixture to about 70 C. until two atoms of chlorine are taken up, and then raising the temperature of the mixture still containing such dehydrochlorination catalyst to a temperature between 140 0. and 200 C. until another molecule of hydrogen chloride is split oil.

9. A process ior producing a carbon compound of the formula C4Cle which comprises treating hexachlorbutene with chlorine at a temperature between 0. and C. in the presence of a chlorination catalyst until two atoms of chlorine are taken up, and heating the resulting octachlorbutane to a temperature between C. and 200 C. in the presence of a dehydrochlorination catalyst until two molecules of hydrogen. chloride are split off.

10. A'process for producing a carbon compound of the formula 0401s which comprises treating hexachlorbutene with chlorine at a temperature between 80 C. and 90 0. in the presence of antimony chloride as a chlorination catalyst until two atoms of chlorine are taken up, and heating the resulting octachlorbutane. to a temperature between 140 C. and 200 C. in the presence of a dehydrochlorination catalyst selected from the group consisting of the chloride compounds of iron, cobalt and manganese until two molecules of hydrogen chloride are split oil. I

11. A process for producing a carbon compound of the formula C4C1e which comprises treating hexachlorbutene with chlorine at a temperature of about 70 C. in the presence of a catalytic material containing ferric chloride as the essential constituent until two atoms of chlorine are taken up and one molecule of hydrogen chloride is split oil, and heating the resulting heptachlorbutene to a temperature of about 200 C. in the presence heating hexachlorbutene at a temperature be- 75 of said catalystuntil another molecule of hydrogen chloride is split oil.

12. A process for producing a carbon compound of the formula C4Cls which comprises treating hexachlorbutene with chlorine at a temperature of about 70 C. in the presence of a catalytic material containing as an essential constituent at least one member of the group of metal chlorides consisting of ferric chloride and antimony chloride until two atoms of chlorine aretaken up and one molecule of hydrogen chloride is split off, and heating the resulting heptachlorbutene to a temperature of about 200 C. in the presence point 0! about -21 0., said compound being stable at temperatures evenabove the boiling of ferric chloride as a dehydrochlorination cat-' point.

MAR'IIN MUGDAN. JOSEF WIMMER. 

